Optical fiber preform

ABSTRACT

An optical fiber preform has a core portion having a first core portion including a central axis, a second core portion disposed around the first core portion, and a third core portion disposed around the second core portion. The first core portion contains 10 atomic ppm or more of an alkali metal and 10 to 600 atomic ppm of chlorine, the second core portion contains 10 atomic ppm or less of the alkali metal and 10 to 600 atomic ppm of chlorine, and the third core portion contains 10 atomic ppm or less of the alkali metal and 2,000 atomic ppm or more of chlorine. An optical fiber has a core region doped with an alkali metal and chlorine, wherein the minimum concentration of chlorine in the core region is 1,000 atomic ppm or more, and the average concentration of the alkali metal therein is 0.2 atomic ppm or more.

This is a divisional application of co-pending prior application Ser.No. 13/441,978, filed on Apr. 9, 2012, which issued as U.S. Pat. No.9,097,834 B2 on Aug. 4, 2015, and which is incorporated by referenceherein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an optical fiber and an optical fiberpreform.

2. Description of the Related Art

An optical fiber composed of silica-based glass and having a core regiondoped with an alkali metal is known. In the case where a core portion ofan optical fiber preform is doped with an alkali metal, it is possibleto reduce the viscosity of the core portion during drawing of theoptical fiber preform, and relaxation of a network structure of silicaglass can be made to enhance. It is believed that, consequently, anattenuation of the resulting optical fiber can be decreased.

Japanese Unexamined Patent Application Publication (Translation of PCTApplication) No. 2005-537210 and U.S. Patent Application Publication No.2006/0130530 disclose a diffusion method as a method of doping silicaglass with an alkali metal. In the diffusion method, a glass pipe isheated by an external heat source or plasma is generated in the glasspipe while vapor of a raw material such as an alkali metal element or analkali metal salt is introduced into the glass pipe, thereby doping aninner surface of the glass pipe with an alkali metal by thermaldiffusion.

After the doping into the inner surface of the glass pipe with thealkali metal in this manner, the glass pipe is heated to be shrunk to acertain diameter. After the glass pipe has been shrunk, in order toremove contaminated impurities, such as Ni, Fe, and other transitionmetals, which were also doped in the glass pipe at the same time as thedoping of the alkali metal, the inner surface of the glass pipe isetched by a certain amount in the direction of the wall thickness. Thediffusion rates of alkali metals are higher than those of transitionmetals. Therefore, even when the transition metals are almost perfectlyremoved by etching the inner surface of the glass pipe by a certainamount in the thickness direction thereof, considerable amount of thedoped alkali metal remains in the glass. After the etching, the glasspipe is made to collapse by heating to manufacture an alkali-metal-dopedcore rod. A cladding portion is synthesized on the outside of thealkali-metal-doped core rod, thus manufacturing an optical fiberpreform. Subsequently, the optical fiber preform is drawn to manufacturean optical fiber.

Japanese Unexamined Patent Application Publication (Translation of PCTApplication) Nos. 2007-504080, 2008-536190, and 2010-501894 describethat a core region of an optical fiber is substantially composed of puresilica glass, that the chlorine concentration is preferably low in anoptical fiber having a core region doped with an alkali metal, and thata pure-silica-core fiber having a germanium-free core region preferablycontains substantially no chlorine and the chlorine concentration of thefiber is preferably 500 ppm by weight or less.

Japanese Unexamined Patent Application Publication (Translation of PCTApplication) No. 2009-541796 discloses an optical fiber having a coreregion containing an alkali metal in a concentration of 50 to 500 ppmand chlorine in an average concentration of 500 ppm by weight or more.However, as is apparent from the description of paragraph [0029] andFIG. 2, the chlorine concentration in a first core region that is mainlydoped with an alkali metal is as low as 100 ppm by weight or less.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an optical fiberhaving a core region doped with an alkali metal, and having a lowattenuation and excellent radiation resistance, and an optical fiberpreform suitable for manufacturing such an optical fiber by drawing.

An optical fiber according to the present invention includes a coreregion and a cladding region surrounding the core region, wherein thecore region is doped with an alkali metal and chlorine, a minimumconcentration of chlorine in the core region is 1,000 atomic ppm (600ppm by weight) or more, and an average concentration of the alkali metalin the core region is 0.2 atomic ppm or more. Herein, the term “atomicppm” refers to the number of atoms of the doped material contained inone million SiO₂ units.

In the optical fiber, the core region preferably further containsfluorine, and an average concentration of a dopant other than the alkalimetal, chlorine, and fluorine in the core region is preferably lowerthan the sum of an average concentration of chlorine and an averageconcentration of fluorine in the core region. The average concentrationof the alkali metal in the core region is preferably 50 atomic ppm orless. The minimum concentration of chlorine in the core region ispreferably 13,000 atomic ppm or less. The core region is preferablydoped with potassium as the alkali metal. An average concentration ofchlorine in the core region is preferably 2,000 atomic ppm or more. Anattenuation of the optical fiber at a wavelength of 1,550 nm ispreferably 0.180 dB/km or less.

In the optical fiber according to the present invention, the minimumconcentration of chlorine in the core region is preferably 2,000 atomicppm or more, the average concentration of chlorine in the core region ispreferably 4,000 atomic ppm or more and 13,000 atomic ppm or less, theaverage concentration of the alkali metal in the core region ispreferably 0.2 atomic ppm or more and 2 atomic ppm or less, the averageconcentration of a dopant other than the alkali metal and halogen in thecore region is preferably lower than the average concentration of thehalogen in the core region, and an attenuation at a wavelength of 1,550nm is preferably 0.180 dB/km or less.

In the optical fiber according to the present invention, after theoptical fiber has been irradiated with gamma rays at a cumulativeradiation dose of 2,000 Gy or more and the irradiation of the gamma rayshas been terminated, a non-relaxation component of an increase in theattenuation at a wavelength of 1,550 nm is preferably 15 dB/km or less.Herein, the term “non-relaxation component of an increase in theattenuation” refers to a difference between an attenuation after 700hours and longer from the termination of irradiation of gamma rays andan attenuation before the start of the irradiation of the gamma rays. Inthe optical fiber according to the present invention, the refractiveindex preferably takes a minimum refractive index N1 of the core regionat a radius r1 smaller than a radius r2 that provides a maximumrefractive index N2 of the core region.

An optical fiber preform according to the present invention includes acore portion to be formed in to a core region of an optical fiber and acladding portion to be formed into a cladding region of the opticalfiber, wherein the core portion has at least a first core portionincluding a central axis, a second core portion disposed in contact withthe outer circumference of the first core portion, and a third coreportion disposed in contact with the outer circumference of the secondcore portion, the first core portion contains an alkali metal in aconcentration of 10 atomic ppm or more and chlorine in a concentrationof 10 to 600 atomic ppm, the second core portion contains the alkalimetal in a concentration of 10 atomic ppm or less and chlorine in aconcentration of 10 to 600 atomic ppm, and the third core portioncontains the alkali metal in a concentration of 10 atomic ppm or lessand chlorine in a concentration of 2,000 atomic ppm or more.

In the optical fiber preform, an average concentration of the alkalimetal in the core portion is preferably 1,000 atomic ppm or less. Afluorine concentration in the third core portion is preferably 200atomic ppm or less. In the optical fiber preform, the refractive indexpreferably takes a minimum refractive index N1 of the core portion at aradius r1 smaller than a radius r2 that provides a maximum refractiveindex N2 of the core portion.

According to the optical fiber of the present invention, a core regionis doped with an alkali metal and thus a low attenuation can beachieved, and at the same time, excellent radiation resistance can alsobe achieved.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between the time (recoverytime) elapsed from the termination of irradiation of gamma-rays and theamount of increase in attenuation of optical fibers at a wavelength of1,550 nm.

FIG. 2 is a graph showing the relationship between the concentration ofpotassium doped to a GeO₂-free core region of the pure silica core fiberand a non-relaxation component of an increase in attenuation of thefiber.

FIG. 3 is a graph showing the relationship between the cumulativeradiation dose and a non-relaxation component of an increase inattenuation.

FIG. 4A is a conceptual view showing distributions of the potassiumconcentration and the chlorine concentration in the radial directionnear a core portion of an optical fiber preform, and FIG. 4B is aconceptual view showing a distribution of the chlorine concentration inthe radial direction near a core region of an optical fiber manufacturedby drawing the optical fiber preform.

FIG. 5 is a graph showing the relationship between the minimum value ofthe chlorine concentration in a core region of an optical fiber and theattenuation at a wavelength of 1,550 nm.

FIG. 6 is a flowchart for explaining an example of a method ofmanufacturing an optical fiber according to an embodiment of the presentinvention.

FIG. 7 is a schematic view illustrating an alkali-metal-doping step in amethod of manufacturing an optical fiber preform.

FIG. 8 is a graph showing an example of a refractive index profile of anoptical fiber preform.

FIG. 9 includes graphs showing other examples of a refractive indexprofile of an optical fiber preform.

FIG. 10 is a graph showing a refractive index profile of an opticalfiber preform.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention will now be described withreference to the drawings. The drawings are illustrative only, and donot limit the scope of the invention. In the drawings, the identicalsymbols indicate the same portions in order to avoid overlapping ofdescription. The proportions of dimensions in the drawings are notnecessarily accurate.

When an alkali metal in silica glass is irradiated with high-energyradiation such as gamma rays, the alkali metal will be able to transferin the glass and causes defects in the glass network structure.Accordingly, when silica glass is doped with a high concentration of analkali metal, the environmental resistance characteristics of the silicaglass are degraded. In actual manufacturing of optical fibers, in thecase where the concentration of an alkali metal is low to the extentthat no problem in terms of environmental resistance characteristicsoccurs, the attenuation may be increased, resulting in a problem of alow yield of optical fibers.

First, the upper limit of the concentration of an alkali metal in a coreregion of an optical fiber will be described. Low-attenuation opticalfibers are used for ultra-long distance transmission, e.g., submarinecables. When the average concentration of an alkali metal in a coreregion of such a low-attenuation optical fiber is higher than 50 atomicppm, radiation resistance, which is an important environmentalresistance characteristic especially for submarine cables, issignificantly degraded. In order to confirm this phenomenon, opticalfibers containing an alkali metal were irradiated with gamma rays from aradiation source of cobalt-60 in a cumulative dose of 2,000 Gy, theirradiation of the gamma rays was then terminated, and the amount ofincrease in the attenuation as compared with the attenuation before thestart of the irradiation was measured.

FIG. 1 is a graph showing the relationship between the time (recoverytime) elapsed from the termination of gamma-ray irradiation of puresilica core fibers, a GeO₂-doped core negative dispersion fiber, and aGeO₂-doped core single-mode fiber and the amount of increase inattenuation at a wavelength of 1,550 nm. The concentration of the alkalimetal in each of the optical fibers was measured by secondary ion massspectrometry (SIMS). Regarding the amount of alkali metal in the opticalfiber denoted by the open circles in the figure, it is believed thatabout 2 atomic ppm of potassium is contained, though the concentrationmay be inaccurate because the measurement lower limit of SIMS is about 1ppm. As shown in FIG. 1, the higher the concentration of potassiumserving as an alkali metal, the larger the increase in the attenuationcaused by the gamma ray irradiation.

Currently, negative dispersion fibers (doped with about 20 ppm by weightof GeO₂) have been practically used as optical fibers for submarinecables. In such a negative dispersion fiber, the amount of increase inthe attenuation after the irradiation of cumulative dose of 2,000 Gy andat a recovery time of 700 hours (i.e., a non-relaxation component of anincrease in the attenuation by gamma-ray irradiation) is about 15 dB/km,and this value is believed to be one standard of radiation resistance.FIG. 2 is a graph showing the relationship between the concentration ofpotassium doped to a GeO₂-free core region in a pure silica core fiberand the non-relaxation component at a wavelength of 1,550 nm after anirradiation of a cumulative dose of 2,000 Gy of gamma rays of the fiber.In order to suppress the non-relaxation component of an increase in theattenuation to be 15 dB/km or less, it is necessary to control theaverage concentration of the alkali metal in the core region of theoptical fiber to be 50 atomic ppm or less. Furthermore, the averageconcentration of the alkali metal in the core region of the opticalfiber is more preferably 2 atomic ppm or less so as to realize radiationresistance substantially equal to that of the standard single-modeoptical fiber having a core region doped with GeO₂.

In addition, in the case where the average concentration of the alkalimetal in the core region is 50 atomic ppm or less, problems regardingreliability such as hydrogen resistance, a strength characteristic ofthe optical fiber, etc. do not occur. For example, regarding hydrogenresistance, the following results were obtained. Optical fibers weretreated at a hydrogen partial pressure of 1 atm (101 kPa) at atemperature of 80° C. for 20 hours. After this hydrogen treatment, theincrease in the attenuation caused by absorption of a hydroxyl (OH)group in a wavelength band of 1.38 μm was 0.0 to 0.15 dB/km. Theincrease in the attenuation was 0.10 dB/km or less in 97% of the opticalfibers, and 0.05 dB/km or less in 50% of the optical fibers. Asignificant increase in the attenuation did not occur in the wavelengthrange of 1,530 to 1,610 nm in all the optical fibers, and thussatisfactory results were obtained. Furthermore, a hydrogen treatmentwas performed at a hydrogen partial pressure of 0.1 atm at a temperatureof 40° C. for three months. During this hydrogen treatment, no abnormalattenuation peak was observed in the wavelength range of 1,420 to 1,610nm Regarding the strength characteristic, both a static fatiguecoefficient (Ns) and a dynamic fatigue coefficient (Nd), which aregenerally known as parameters indicating a failure probability of anoptical fiber, were in the range of 18 to 27 and thus satisfactoryresults were obtained.

FIG. 3 is a graph showing the relationship between the cumulativeradiation dose and the non-relaxation component of an increase in theattenuation at a wavelength of 1,550 nm of an optical fiber, which is apure silica core fiber having a core doped with potassium in an averageconcentration of about 2 atomic ppm. With an increase in the cumulativeradiation dose, the non-relaxation component increases. It is estimatedthat an optical fiber that is actually laid as a submarine cablereceives a cumulative radiation dose of about 0.01 Gy for a period ofabout 20 years, and that the increase in the attenuation in this case ispreferably 0.005 dB/km or less. Regarding an optical fiber having a coredoped with potassium in an average concentration of about 2 atomic ppm,when the optical fiber receives a cumulative radiation dose of 0.01 Gy,the amount of increase in the attenuation at a wavelength of 1,550 nm isestimated to be 0.002 dB/km or less by extrapolating the relationshipbetween the cumulative radiation dose and the non-relaxation component.However, in the case where the concentration of an alkali metal in acore region of an optical fiber is lower than that (50 to 500 ppm) ofthe optical fiber described in the above related art document, theattenuation of the optical fiber may not be decreased.

Next, an effect of doping chlorine to an optical fiber will bedescribed. The related art document describes that codoping of an alkalimetal and chlorine in silica-based glass should be avoided because analkali chloride is produced and thus the silica-based glass iscrystallized. However, the inventor of the present invention found thefollowing: Regarding an optical fiber preform, the presence of an alkalichloride should be avoided because the alkali chloride may causecrystallization and formation of air bubbles. In contrast, regarding anoptical fiber, when a core region of the optical fiber contains 1,000atomic ppm or more of chlorine, the attenuation is decreased.Specifically, the inventor of the present invention found that thechlorine concentration should be low in an optical fiber preform,whereas the chlorine concentration should be high in an optical fiber.

The inventor of the present invention found that it is desirable tostart from an optical fiber preform having a core portion including,from the center, a first core portion, a second core portion, and athird core portion in that order, wherein, in the first core portion,the alkali metal concentration is high and the chlorine concentration islow, in the third core portion, the alkali metal is not substantiallycontained and the chlorine concentration is high, and in the second coreportion located between the first core portion and the third coreportion, both the alkali metal concentration and the chlorineconcentration are low, and to draw the optical fiber preform underappropriate conditions. Regarding the drawing conditions, for example,the drawing speed (take-up speed for the optical fiber) may be set to1,000 to 3,000 m/min, the drawing tension (tension applied to the glassportion of an optical fiber) may be set to 30 to 150 gf (0.3 to 1.5 N),and the time spent in a drawing apparatus in the form of an opticalfiber having a glass diameter of 200 μm or less may be set to 0.01 to0.3 seconds. The diameter of the optical fiber preform may be 70 to 180mm, and the diameter of the glass portion of the optical fiber may be100 to 150 μm.

FIG. 4A is a conceptual view showing distributions of the potassiumconcentration (solid line) and the chlorine concentration (broken line)in the radial direction near a core portion of an optical fiber preform.In this example, the core portion of the optical fiber preform was dopedwith potassium as an alkali metal so that the maximum concentration ofpotassium was about 800 atomic ppm and the average concentration ofpotassium in the core portion was about 10 atomic ppm. Regarding theconditions for drawing this optical fiber preform, the drawing speed wasset to 1,300 m/min, the drawing tension was set to 70 gf, and the timespent in a drawing apparatus in the form of a fiber having a glassdiameter of 200 μm or less was set to about 0.05 seconds.

FIG. 4B is a conceptual view showing a distribution of the chlorineconcentration in the radial direction near a core region of an opticalfiber manufactured by drawing the optical fiber preform in FIG. 4A. Inthis optical fiber, potassium diffused from the first core portion, andpotassium could not be detected with SIMS over the entire area of across section of the optical fiber. Thus, the potassium concentrationwas decreased to 10 atomic ppm or less. This optical fiber was asingle-mode fiber at a wavelength of 1,550 nm. In this optical fiber,the minimum concentration of chlorine in the core region was 3,000atomic ppm, the average concentration of chlorine over the entire coreregion was 7,000 atomic ppm, and the attenuation at a wavelength of1,550 nm was 0.163 dB/km. On the other hand, as a comparative example,an optical fiber having substantially the same potassium concentrationas that of the optical fiber in FIG. 4B was manufactured under the sameconditions. In this comparative example, in the case where the minimumconcentration of chlorine over the entire core region was set to 100atomic ppm, and the average concentration thereof was set to 300 atomicppm, the attenuation was very high, i.e., 0.215 dB/km.

A reason in the decrease in attenuation is supposed to be as follows. Inthe case where no alkali metal is present, there was no significantdifference in the distribution of the chlorine concentration between anoptical fiber preform and the resulting optical fiber. In contrast, inthe optical fiber (FIG. 4B) manufactured by drawing the optical fiberpreform in FIG. 4A, the chlorine concentration near the center of thecore increased to several thousand atomic ppm, showing that chlorine inan amount 100 times or more of the alkali metal transferred.Accordingly, it is believed that, although glass defects may be formedby thermal diffusion of a small amount of alkali metal during drawingprocess and may cause an increase in attenuation, the glass defects arerepaired by diffused chlorine elements, and thus the increase inattenuation can be suppressed. In addition, since an optical fiber has asmall diameter, the cooling rate after heating in a drawing step is veryhigh. Therefore, even when an alkali metal salt is present, thesilica-based glass may not crystallize significantly. This is alsobelieved to be a factor in the decrease in attenuation.

Next, conditions of the concentration of doped chlorine will bedescribed. FIG. 5 is a graph showing the relationship between theminimum value of the chlorine concentration in a core region of anoptical fiber and the attenuation at a wavelength of 1,550 nm. Thechlorine concentration in the core region in the optical fiber wasmeasured with electron probe microanalysis (EPMA). In this example, acore portion of an optical fiber preform was doped with potassium as analkali metal in a maximum concentration of about 1,000 atomic ppm and anaverage concentration of about 20 atomic ppm in the core portion.Regarding the conditions for drawing the optical fiber preform, thedrawing speed was set to 1,700 m/min, the drawing tension was set to 50gf, and the time spent in a drawing apparatus in the form of an opticalfiber having a glass diameter of 200 μm or less was set to about 0.04seconds.

The potassium concentration in the core region of the optical fibermanufactured by drawing the above optical fiber preform was estimated tobe about 1 atomic ppm on average. However, potassium could not bedetected over the entire area of a cross section of the optical fiber bythe measurement with SIMS. The optical fiber was a single-mode fiber ata wavelength of 1,550 nm.

As is apparent from FIG. 5, when the chlorine concentration is 1,000atomic ppm or less, the attenuation of the optical fiber tends todrastically increase. Thus, the minimum concentration of chlorine in thecore region of the optical fiber is preferably 1,000 atomic ppm or more.The minimum concentration of chlorine in the core region of the opticalfiber is more preferably 2,000 atomic ppm or more because a lowattenuation can be stably realized at a chlorine concentration of 2,000atomic ppm or more.

As shown in FIGS. 4A and 4B, the chlorine concentration in the opticalfiber preform is very low near the central portion of the core portion,whereas the chlorine concentration in the optical fiber is the lowestnear the central portion of the core region and is high at the outerperipheral portion of the core region. The average concentration ofchlorine in the entire core region becomes twice or more than theminimum concentration thereof. Accordingly, the average concentration ofchlorine in the core region of the optical fiber is preferably 2,000atomic ppm or more, and more preferably 4,000 atomic ppm or more.

Next, the lower limit of the concentration of doped potassium will bedescribed. An optical fiber preform has a core portion doped with analkali metal and having a diameter of about several millimeters. In astep (drawing step) of drawing the optical fiber preform is heated at1,800° C. or higher to manufacture an optical fiber having a core regionhaving a diameter of about several micrometers, thus the alkali metaldiffuses in a significant distance. The diffusion distance of the alkalimetal in the drawing step is determined on the basis of the heatingtemperature of the optical fiber preform, the drawing speed in thedrawing step, the apparatus used in the drawing step, e.g., a furnacelength, and other drawing conditions. It was found that when drawing isperformed under the conditions of a drawing speed of 1,000 to 3,000m/min, a drawing tension of 50 to 150 gf, and a time spent in a drawingapparatus in the form of a fiber having a glass diameter of 200 μm orless of 0.01 to 0.3 seconds, an alkali metal present only in the coreportion in the optical fiber preform widely diffuses to a claddingportion, for example, diffuses over a range of about 30 μm in diameterin an optical fiber having a core diameter of 8 μm, and the averageconcentration of the alkali metal in the core region of the opticalfiber is reduced to about 1/20 of the average concentration in theoptical fiber preform.

Furthermore, it was found that the attenuation of an optical fiberdecreases even when the average concentration of an alkali metal is lowto the extent that the average concentration cannot be measured by acurrently used measurement method, such as SIMS, EPMA, or inductivelycoupled plasma-mass spectrometry (ICP-MS), which has a lower limit ofdetection of about 1 ppm. It was also found that even when the averageconcentration of an alkali metal in a core portion of an optical fiberpreform is about 5 atomic ppm, the attenuation at a wavelength of 1.55μm can be significantly decreased to 0.175 dB/km or less as long as theminimum value of the chlorine concentration in the resulting opticalfiber is 1,500 atomic ppm or more.

If it is supposed that the concentration of the alkali metal in the coreregion of the optical fiber is reduced to about 1/20 of theconcentration in the optical fiber preform as described above, theaverage concentration of the alkali metal in the core region of theoptical fiber is preferably 0.2 atomic ppm or more. More preferably, theaverage concentration of the alkali metal in the core portion of theoptical fiber preform is about 10 atomic ppm, and the averageconcentration of the alkali metal in the core region of the opticalfiber is 0.5 atomic ppm or more because the attenuation of the opticalfiber at a wavelength of 1,550 nm can be decreased to 0.165 dB/km orless.

On the other hand, since the average concentration of the alkali metalin the core region of the optical fiber is preferably 50 atomic ppm orless, as described above, the average concentration of the alkali metalin the core portion of the optical fiber preform is preferably about1,000 atomic ppm or less. Also, since the average concentration of thealkali metal in the core region of the optical fiber is more preferably2 atomic ppm or less, as described above, the average concentration ofthe alkali metal in the core portion of the optical fiber preform ismore preferably about 40 atomic ppm or less.

Next, the structure of the optical fiber preform according to thisembodiment, and a method of manufacturing an optical fiber according tothis embodiment will be described. If an alkali metal salt is producedin the optical fiber preform, cristobalite and air bubbles tend to begenerated. To prevent this problem, the optical fiber preform preferablyhas a first core portion having a low chlorine concentration in an areadoped with a high concentration of an alkali metal. In order to increasethe chlorine concentration in the entire core portion, the optical fiberpreform preferably has a third core portion that is not substantiallydoped with the alkali metal and that is doped with a high concentrationof chlorine, the third core portion being disposed in an outerperipheral portion of the first core portion. Furthermore, in order tosuppress the generation of an alkali metal salt due to a mutualdiffusion between the alkali metal and chlorine in a step ofmanufacturing the preform, the optical fiber preform preferably has asecond core portion having a low concentration of the alkali metal and alow concentration of chlorine, the second core portion being disposedbetween the first core portion and the third core portion.

More specifically, a core portion of the optical fiber preformpreferably has, from the center, a first core portion, a second coreportion, and a third core portion in that order, wherein the first coreportion contains an alkali metal in a concentration of 10 atomic ppm ormore and chlorine in a concentration of 10 to 600 atomic ppm, the secondcore portion contains the alkali metal in a concentration of 10 atomicppm or less and chlorine in a concentration of 10 to 600 atomic ppm, andthe third core portion contains the alkali metal in a concentration of10 atomic ppm or less and chlorine in a concentration of 2,000 atomicppm or more.

The chlorine concentration in each of the first core portion and thesecond core portion is more preferably 10 to 200 atomic ppm. Each of thefirst core portion and the second core portion may be doped with 3,000to 15,000 atomic ppm of fluorine. Preferably, the third core portion hasa fluorine concentration of 200 atomic ppm or less and substantiallydoes not contain fluorine in order to keep the refractive index of thecore portion high. The core portion may further contain other halogenand oxygen molecules.

The core portion preferably does not substantially contain transitionmetals such as Fe, Ni, and Cu, and the average concentration of thetransition metals in the entire core portion is preferably 10 ppb orless. Similarly, the concentration of an OH group in the core portion ispreferably low, specifically, 100 ppb or less. Preferably, the coreportion does not contain, for example, Ge or P, and the averageconcentration of a dopant other than the alkali metal and the halogen ispreferably lower than the average concentration of the halogen in thecore portion. A cladding portion has a refractive index lower than thatof the third core portion and is preferably composed of silica-basedglass doped with fluorine.

FIG. 6 is a flowchart for explaining an example of a method ofmanufacturing an optical fiber according to an embodiment of the presentinvention. An optical fiber preform having a first core portion, asecond core portion, a third core portion, and a cladding portion, andan optical fiber can be manufactured by sequentially performing steps S1to S9.

In step S1, a silica-based glass pipe is prepared. The chlorineconcentration of this glass pipe is preferably 600 atomic ppm or less,and preferably 100 atomic ppm or less so as not to produce an alkalimetal salt in an optical fiber preform.

In step S2, an inner surface of the glass pipe is doped with an alkalimetal by thermal diffusion. FIG. 7 is a conceptual view illustrating analkali-metal-doping step in the method of manufacturing an optical fiberpreform. Gas of a raw material 3 for an alkali metal heated by a heatsource (such as an electric furnace or a burner) 2 is supplied to theinside of a glass pipe 1 together with a carrier gas (such as O₂ gas, Argas, or He gas) supplied from a supply source (not shown). At the sametime, the glass pipe 1 is heated by an external heat source (such as athermal plasma or an oxyhydrogen flame) 4. Thus, the glass pipe 1 isdoped with the alkali metal by thermal diffusion from the inner surfacethereof.

In step S3, the diameter of the glass pipe is shrunk by heating theglass pipe. In step S4, the inner surface of the glass pipe is etched soas to remove impurities such as Ni, Fe, other transition metals, and OHgroups, which are also doped to the glass pipe at the same time as thedoping of the alkali metal. In step S5, the glass pipe is collapsed toprepare a glass rod. A central portion of this glass rod functions as afirst core portion. In step S6, the outer peripheral surface of theglass rod is ground by a certain amount to remove impurities such astransition metals and OH groups. Consequently, the peripheral portion ofthe glass rod functions as a second core portion in which the alkalimetal concentration and the chlorine concentration are low.

In step S7, a third core portion is formed on the outer periphery of theglass rod to prepare a core glass rod. The third core portion is formedby synthesizing silica-based glass doped with a high concentration,i.e., 2,000 atomic ppm or more of chlorine. In step S8, a claddingportion is formed on the outer periphery of the third core portion ofthe core glass rod to manufacture an optical fiber preform. Thiscladding portion is composed of silica glass having a refractive indexlower than that of the third core portion.

When the outer diameter of the first core portion of the optical fiberpreform is represented by D1, the outer diameter of the second coreportion is represented by D2, and the outer diameter of the third coreportion is represented by D3, a ratio D3/D1 is preferably in the rangeof 2 to 10, and a ratio D2/D1 is preferably in the range of 1.1 to 6.The maximum value of the relative refractive index difference

${\Delta\; n} = \frac{n - n_{cladding}}{n_{cladding}}$in the third core portion relative to the minimum refractive indexn_(cladding) of the cladding portion is preferably in the range of 0.15%to 1.0%.

Regarding an optical fiber preform having the above-describeddistributions of the chlorine concentration and the fluorineconcentration in the radial direction, a refractive index near thecentral axis of the core portion is low, and a refractive index in theouter periphery of the central portion is high. Specifically, therefractive index takes a minimum refractive index N1 at a radius r1smaller than a radius r2 that provides a maximum refractive index N2 ofthe core portion.

In doping with an alkali metal by thermal diffusion, if the silica-basedglass pipe contains fluoride and has lower refractive index than that ofa pure silica glass, the alkali metal and fluorine react with each otherto generate an alkali fluoride. This alkali fluoride is desorbed fromthe inner surface of the glass pipe, which may result in an increase inthe refractive index of the inner surface of the glass pipe.Accordingly, in the glass rod obtained by collapsing this glass pipe,the glass rod being doped with the alkali metal, the refractive indexnear the central portion may be higher than the minimum value.Specifically, when the refractive index at the central axis (r=0) of thecore portion of the optical fiber preform is represented by N3, therelationship N1<N3<N2 may be satisfied (refer to FIG. 8).

In step S9, an optical fiber is manufactured by drawing the opticalfiber preform. The refractive index distribution of the optical fiber inthe radial direction is changed from the refractive index distributionof the optical fiber preform by thermal diffusion of chlorine andfluorine in a heating step such as a drawing step and depending on thedistribution of a residual stress in the optical fiber. However, as inthe optical fiber preform, regarding the refractive index distributionof the optical fiber, the refractive index takes a minimum refractiveindex N1 at a radius r1 smaller than a radius r2 that provides a maximumrefractive index N2 of the core region. In addition, when the refractiveindex at the central axis (r=0) of the core region is represented by N3,the relationship N1<N3<N2 may be satisfied.

Herein, the optical fiber preform may be an intermediate product of anoptical fiber preform, and silica-based glass may be further synthesizedon the outer periphery of the intermediate product. Each of the coreportion and the cladding portion of the optical fiber preform may have aradial distribution of the refractive index. For example, each of thecore portion and the cladding portion may have any of the refractiveindex profiles illustrated in FIG. 9, but the refractive index profileis not limited thereto. Note that, in the refractive index profile of anoptical fiber preform illustrated in FIG. 10, the refractive index at aposition spaced away from a central axis of the optical fiber preform bya distance r in the radial direction is represented by N(r). It isassumed that the refractive index N(L) becomes the maximum value N_(max)at a position L in the radial direction. In addition, it is assumedthat, at a position R in the radial direction where |L|<|R|,(N_(max)−N(R))/N_(max) is 0.15%. The region within the radius R in thiscase is defined as the core portion.

The attenuation of the optical fiber at a wavelength of 1,550 nm ispreferably low. Specifically, the attenuation at a wavelength of 1,550nm is preferably 0.180 dB/km or less, more preferably, 0.170 dB/km orless, and still more preferably 0.160 dB/km or less. The effective areamay be about 70 to 160 μm² at a wavelength of 1,550 nm. The chromaticdispersion at a wavelength of 1,550 nm may be +15 to +22 ps/nm/km. Theattenuation at a wavelength of 1,380 nm is preferably low. Specifically,the attenuation at a wavelength of 1,380 nm is preferably 0.8 dB/km orless, more preferably, 0.4 dB/km or less, and most preferably 0.3 dB/kmor less. The polarization mode dispersion at a wavelength of 1,550 nmmay be 0.2 ps/√km or less. The cable cut-off wavelength is preferably1,520 nm or less, and more preferably 1,450 nm, which is a pumpwavelength used in Raman amplification, or less. The diameter of thecore portion is about 5 to 15 μm. The relative refractive indexdifference between the core portion and the cladding portion:

$\frac{\begin{matrix}{\left( {{refractive}\mspace{14mu}{index}\mspace{14mu}{of}\mspace{14mu}{core}\mspace{14mu}{portion}} \right) -} \\\left( {{refractive}\mspace{14mu}{index}\mspace{14mu}{of}\mspace{14mu}{cladding}\mspace{14mu}{portion}} \right)\end{matrix}}{{refractive}\mspace{14mu}{index}\mspace{14mu}{of}\mspace{14mu}{core}\mspace{14mu}{portion}}$is about 0.1% to 0.7%.

Example 1

In Example 1, an optical fiber preform and an optical fiber weremanufactured by sequentially performing the processes of steps S1 to S9in FIG. 6, and transmission characteristics of the optical fiber wereevaluated.

A glass pipe prepared in step S1 was composed of silica-based glasscontaining 100 atomic ppm of chlorine and 6,000 atomic ppm of fluorineas dopants, and the concentration of other impurities in the glass pipewas 10 ppm or less. Thus, the glass pipe was substantially composed ofpure silica glass. The outer diameter of this glass pipe was 35 mm, andthe inner diameter thereof was about 20 mm.

In step S2, potassium bromide (KBr) was used as a raw material for analkali metal, and this raw material was heated to a temperature of 840°C. by a heat source to generate KBr vapor. The glass pipe was thenheated by a thermal plasma flame serving as an external heat source sothat the temperature of the outer surface of the glass pipe became2,050° C. while the KBr vapor was introduced into the glass pipetogether with oxygen introduced as a carrier gas at a flow rate of 1SLMi (1 liter/min in terms of the standard state). Heating was performedby causing the thermal plasma flame to traverse at a rate of 30 mm/minfor 20 turns. Thus, the inner surface of the glass pipe was doped withpotassium by thermal diffusion.

In step S3, the glass pipe doped with potassium was heated by a thermalplasma flame serving as an external heat source so that the temperatureof the outer surface of the glass pipe became 2,100° C. while oxygen (2SLM) was supplied through the glass pipe. Heating was performed bycausing the thermal plasma flame to traverse at a rate of 40 mm/min for6 turns. The inner diameter of the glass pipe doped with potassium wasreduced to 3 mm.

In step S4, gas-phase etching was performed by heating the glass pipedoped with potassium by an external heat source while SF₆ (0.05 SLM) andoxygen (1 SLM) were introduced into the glass pipe. Thus, the innerdiameter of the glass pipe was made to be 3.4 mm.

In step S5, the absolute pressure in the glass pipe was reduced to 1 kPawhile oxygen (1 SLM) was introduced into the glass pipe, and the glasspipe was made to collapse by increasing the surface temperature of theglass pipe to 1,400° C. by an external heat source. Thus, analkali-metal-doped core glass rod having a diameter of 28 mm wasobtained. The maximum potassium concentration of this alkali-metal-dopedcore glass rod was 1,800 atomic ppm. A region (first core portion) dopedwith 10 atomic ppm or more of potassium had a diameter of 12 mm.

In step S6, the alkali-metal-doped core glass rod was elongated by aknown method so as to have a diameter of 20 mm. The outer peripheralportion of the alkali-metal-doped core glass rod was then ground so thatthe diameter of the glass rod was reduced to 12 mm. In the resultingcore glass rod, a ratio D2/D1 of the outer diameter (D2) of a secondcore portion in which both the alkali metal concentration and thechlorine concentration were low to the diameter (D1) of the first coreportion doped with the alkali metal was 1.4.

In step S7, silica-based glass (third core portion glass) doped with10,000 atomic ppm of chlorine was provided on the outside of thealkali-metal-doped core glass rod to prepare a core glass rod having anouter diameter of 60 mm. The alkali-metal-doped core glass and the outercore glass constitute a core portion of an optical fiber preform. Thealkali metal concentration of this core portion was 30 atomic ppm onaverage. The synthesis of this third core portion was performed by aknown rod-in-collapse method in which a silica-based glass pipe dopedwith 10,000 atomic ppm of chlorine was prepared, the alkali-metal-dopedcore glass rod was inserted into the glass pipe, and the glass pipe andthe alkali-metal-doped core glass rod were heated and integrated witheach other by an external heat source. In the resulting core glass rod,a ratio D3/D1 of the outer diameter (D3) of the third core portion dopedwith a high concentration of chlorine to the diameter (D1) of the firstcore portion doped with the alkali metal was 7.0.

In step S8, silica-based glass (optical cladding glass portion) dopedwith fluorine was synthesized on the outside of the resulting core glassrod. The relative refractive index difference between the third coreportion and the optical cladding portion was about 0.35% at the maximum.The synthesis of this optical cladding glass portion was performed by aknown rod-in-collapse method in which a silica-based glass pipe dopedwith 27,000 atomic ppm of fluorine was prepared, the core glass rod wasinserted into the glass pipe, and the glass pipe and the core glass rodwere heated and integrated with each other by an external heat source.

Furthermore, the glass rod having the optical cladding was subjected toelongation or the like so as to have a predetermined diameter.Silica-based glass (physical cladding glass portion) doped with fluorinewas then synthesized on the outside of the glass rod to prepare anoptical fiber preform having a diameter of 140 mm. The relativerefractive index difference between the third core portion and thephysical cladding portion was about 0.33% at the maximum. The synthesisof this physical cladding glass portion was performed by a known sootmethod (vapor-phase axial deposition (VAD) method in this example).

In step S9, the optical fiber preform was drawn to manufacture anoptical fiber. In this step, the drawing speed was 2,300 m/min, thedrawing tension was 50 gf, and the time spent in a drawing apparatus inthe form of a fiber having a glass diameter of 200 μm or less was 0.02seconds. Characteristics of the optical fiber manufactured as describedabove are shown in Table. An optical fiber having a low attenuation wasobtained.

TABLE Example 1 Example 2 Minimum value of chlorine atomic 2,800 3,300concentration ppm Concentration of potassium doped atomic about 2 1 orless (average in core) ppm Attenuation (wavelength: 1,300 nm) dB/km0.285 0.290 Attenuation (wavelength: 1,380 nm) dB/km 0.283 0.320Attenuation (wavelength: 1,550 nm) dB/km 0.160 0.161 Chromaticdispersion (wavelength: ps/nm/km +15.9 +20.9 1,550 nm) Dispersion slope(wavelength: ps/nm²/km +0.054 +0.060 1,550 nm) Zero-dispersionwavelength nm 1,310 Dispersion slope at zero-dispersion ps/nm²/km +0.083wavelength Effective area (wavelength: μm² 82 140 1,550 nm) Mode fielddiameter (wavelength: μm 10.3 12.7 1,550 nm) Mode field diameter(wavelength: μm 9.1 1,310 nm) Fiber cut-off wavelength (2 m) nm 1,3101,590 Cable cut-off wavelength (22 m) nm 1,230 1,490 Polarization modedispersion (C- ps/√km 0.11 0.01 and L-bands) Nonlinear coefficient(wavelength: (W · km)⁻¹ 1.1 0.6 1,550 nm, random polarization state)

Example 2

In Example 2, an optical fiber preform and an optical fiber weremanufactured by sequentially performing the processes of steps S1 to S9in FIG. 6, and transmission characteristics of the optical fiber wereevaluated.

A glass pipe prepared in step S1 was composed of silica-based glasscontaining 50 atomic ppm of chlorine and 7,000 atomic ppm of fluorine asdopants, and the concentration of other impurities in the glass pipe was10 ppm or less. Thus, the glass pipe was substantially composed of puresilica glass. The outer diameter of this glass pipe was 25 mm, and theinner diameter thereof was about 10 mm.

In step S2, potassium bromide (KBr) was used as a raw material for analkali metal, and this raw material was heated to a temperature of 800°C. by a heat source to generate KBr vapor. The glass pipe was thenheated by an oxyhydrogen flame serving as an external heat source sothat the temperature of the outer surface of the glass pipe became2,050° C. while the KBr vapor was introduced into the glass pipetogether with oxygen introduced as a carrier gas at a flow rate of 1SLM. Heating was performed by causing the oxyhydrogen flame to traverseat a rate of 30 mm/min for 15 turns. Thus, the inner surface of theglass pipe was doped with potassium by thermal diffusion.

In step S3, the glass pipe doped with potassium was heated by aoxyhydrogen flame serving as an external heat source so that thetemperature of the outer surface of the glass pipe became 2,100° C.while oxygen (2 SLM) was supplied through the glass pipe. Heating wasperformed by causing the oxyhydrogen flame to traverse at a rate of 40mm/min for 8 turns. The inner diameter of the glass pipe doped withpotassium was reduced to 3 mm.

In step S4, gas-phase etching was performed by heating the glass pipedoped with potassium by an external heat source while SF₆ (0.05 SLM) andoxygen (1 SLM) were introduced into the glass pipe. Thus, the innerdiameter of the glass pipe was made to be 3.3 mm.

In step S5, the absolute pressure in the glass pipe was reduced to 1 kPawhile oxygen (1 SLM) was introduced into the glass pipe, and the glasspipe was made to collapse by increasing the surface temperature of theglass pipe to 1,400° C. by an external heat source. Thus, analkali-metal-doped core glass rod having a diameter of 22 mm wasobtained. The maximum potassium concentration of this alkali-metal-dopedcore glass rod was 1,300 atomic ppm. A region (first core portion) dopedwith 10 atomic ppm or more of potassium had a diameter of 7 mm.

In step S6, the alkali-metal-doped core glass rod was elongated by aknown method so as to have a diameter of 16 mm. The outer peripheralportion of the alkali-metal-doped core glass rod was then ground so thatthe diameter of the glass rod was reduced to 10 mm. In the resultingcore glass rod, a ratio D2/D1 of the outer diameter (D2) of a secondcore portion in which both the alkali metal concentration and thechlorine concentration were low to the diameter (D1) of the first coreportion doped with the alkali metal was 2.0.

In step S7, silica-based glass (third core portion glass) doped with13,000 atomic ppm of chlorine was provided on the outside of thealkali-metal-doped core glass rod to prepare a core glass rod having anouter diameter of 30 mm. The alkali-metal-doped core glass and the outercore glass constitute a core portion of an optical fiber preform. Thealkali metal concentration of this core portion was 10 atomic ppm onaverage. The synthesis of this third core portion was performed by aknown rod-in-collapse method in which a silica-based glass pipe dopedwith 13,000 atomic ppm of chlorine was prepared, the alkali-metal-dopedcore glass rod was inserted into the glass pipe, and the glass pipe andthe alkali-metal-doped core glass rod were heated and integrated witheach other by an external heat source. In the resulting core glass rod,a ratio D3/D1 of the outer diameter (D3) of the third core portion dopedwith a high concentration of chlorine to the diameter (D1) of the firstcore portion doped with the alkali metal was 5.9.

In step S8, silica-based glass (optical cladding glass portion) dopedwith fluorine was synthesized on the outside of the resulting core glassrod. The relative refractive index difference between the third coreportion and the optical cladding portion was about 0.29% at the maximum.Furthermore, the glass rod having the optical cladding was subjected toelongation or the like so as to have a predetermined diameter.Silica-based glass (physical cladding glass portion) doped with fluorinewas then synthesized on the outside of the glass rod to prepare anoptical fiber preform having a diameter of 90 mm. The relativerefractive index difference between the third core portion and thephysical cladding portion was about 0.23% at the maximum.

In step S9, the optical fiber preform was drawn to manufacture anoptical fiber. In this step, the drawing speed was 1,000 m/min, thedrawing tension was 50 gf, and the time spent in a drawing apparatus inthe form of a fiber having a glass diameter of 200 μm or less was 0.05seconds.

Characteristics of the optical fiber manufactured as described above areshown in Table above. An optical fiber having a low attenuation wasobtained.

What is claimed is:
 1. An optical fiber preform comprising: a coreportion to be formed into a core region of an optical fiber, the coreportion having a first core portion that includes a central axis andthat has an alkali metal concentration of 10 atomic ppm or more and achlorine concentration of between 10 to 600 atomic ppm, a second coreportion that is disposed in contact with the outer circumference of thefirst core portion, that has no/zero alkali metals or has an alkalimetal concentration of which is 10 atomic ppm or less, and that haschlorine concentration of which is between 10 to 600 atomic ppm, and athird core portion that is disposed in contact with the outercircumference of the second core portion, that has no/zero alkali metalsor has an alkali metal concentration of which is 10 atomic ppm or less,and that has chlorine concentration of which is 2,000 atomic ppm ormore; and a cladding portion to be formed into a cladding region of theoptical fiber.
 2. The optical fiber preform according to claim 1,wherein an average concentration of the alkali metal in the core portionis 1,000 atomic ppm or less, and wherein the average concentration ofthe alkali metal in the core portion is more than and not equal to 0atomic ppm.
 3. The optical fiber preform according to claim 1, wherein afluorine concentration in the third core portion is 200 atomic ppm orless, and wherein the fluorine concentration in the third core portionincludes 0 atomic ppm.
 4. The optical fiber preform according to claim1, wherein the refractive index takes a minimum refractive index N1 ofthe core portion at a radius r1 smaller than a radius r2 that provides amaximum refractive index N2 of the core portion.
 5. The optical fiberpreform according to claim 1, wherein the core portion has a refractiveindex N3 at the central axis and the refractive indices N1, N2, and N3satisfy a relationship N1<N3<N2.
 6. The optical fiber preform accordingto claim 1, wherein the cladding portion has a refractive index lowerthan a refractive index of the third core portion.
 7. The optical fiberpreform according to claim 1, wherein the third core portion has arefractive index n and the cladding portion has a minimum refractiveindex n_(cladding) and a maximum value of a relative refractive indexdifference ${\Delta\; n} = \frac{n - n_{cladding}}{n_{cladding}}$ is inthe range of between 0.15% to 1.0%.
 8. The optical fiber preformaccording to claim 1, wherein the first core portion has an outerdiameter D1 and the second core portion has an outer diameter D2 and aratio D2/D1 is in the range of between 1.1 to
 6. 9. The optical fiberpreform according to claim 1, wherein the first core portion has anouter diameter D1 and third core portion has an outer diameter D3 and aratio D3/D1 is in the range of between 2 to 10.